O-ethyl-s-(n)-propyl-s-carbamoylalkyl dithiophosphates

ABSTRACT

S-carbamoylalkyl-O-ethyl-S-(n)-propyldithiophosphoric esters having the formula   wherein R1represents hydrogen, methyl or allyl and R2 represents -CH2OCH3, -C2H4OCH3, -C3H6OCH3, -CH2CN, C2H4CN, -OCH3or allyl a process for their manufacture and their use in pest control.

United States Patent [1 1 Beriger Nov. 18, 1975 O-ETHYL-S-(N)-PROPYL-S- CARBAMOYLALKYL DITHIOPHOSPHATES [75] Inventor: Ernst Beriger, Allschwil,

Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Aug. 9, 1974 [21] App]. No.: 495,933

Related U.S. Application'Data [62] Division of Ser. No. 315,973. Dec. 19, 1972, Pat. No.

[30] Foreign Application Priority Data Dec. 24, 1971 Switzerland 18909/71 Jan. 3, 1972 Switzerland 16041/72 [52] US. Cl 260/943; 424/211 [51] Int. Cl. C07F 9/165; AOlN 9/36 [58] Field of Search 260/943 [56] References Cited UNITED STATES PATENTS 3,350,192 Richter 7. 260/943 X Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-Frederick H. Rabin [57] ABSTRACT S-carbamoylalkyl-O-ethyl-S-(n)-propyldithiophosphoric esters having the formula 1 Claim, No Drawings O-ETHYL-S-(N )-PROPYL-S-CARBAMOYLALKYL DITHIOPHOSPHATES wherein R represents hydrogen, methyl or allyl and R represents CH OCI-I C I-l,,OCI-I C I-I OCH CI-I CN, C I-I CN, OCI-I or allyl.

The compounds of the formula I can be manufacutred by methods which are known per se, e.g. as follows:

(XV) 1 (IX) In the formulae II to XV, R and R have the meanings given for the formula I and R representsa lower alkyl radical, X represents oxygen or sulphur, Hal represents fluorine, chlorine, bromine or iodine, in particular chlorine, and Me represents ammonium, alkylam- 2 monium or an alkali metal. Processes l, 2 and 3 can be carried out at normal pressure, at a temperature of 80C, preferably 2050C, and in solvents and diluents which are inert towards the reactants.

5 Examples of suitable solvents or diluents are: ether and ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, tetrahydrofuran; amides, such as N,N-dialkylated carboxylid amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene,

toluene, xylenes, chloroform, chlorobenzene; nitriles,

such as acetonitrile.

Some of the starting materials of the formulae II, III and IV are known or they can be manufactured by methods analogous to those known in the art.

The active substances of the formula I are suitable for combating animal and plant pests of the most diverse kinds and can be used partly as well for regulating growth, as abscission agents and defoliants.

The insecticidal action of analogous compounds is disclosed in the literature, but by comparison the compounds of the formula I have surprisingly a markedly stonger and more lasting action against all development stages, such as eggs, nymphs, pupae and adults, of insects, such for example as those of the families:

Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae.

The compounds of the formula I also act against eggs, larvae and adults of representatives of the order Acarina, such as mites, spider mites and ticks, e.g. of the families Ixodidae, Argasidae, Tetranychidae and Demanyssidae.

By addition of other insecticides and/or acaricides it is possible to broaden substantially the insecticidal or acaricidal action and to adapt it to given circumstances.

The following active substances are examples of suitable additives:

ORGANIC PI-IOSPI-IORUS COMPOUNDS (DICHLOR- Z-[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]-phenyl-N-methylcarbamate CHLORINATED HYDROCARBONS 'y-hexachlorocyclohexane [GAMMEXANE; LIN- DAN; 'yl-lCl-l] l,2,4,5 ,6,7,8,8-octachloro-3a,4,7,7a'tetrahydro-4,7-

methylene indane [CHLORDAN] 1,4,5 ,6,7,8,8-heptachloro,3a,4,7,7a-tetrahydro-4,7-

methylene indane [HEPTACHLOR] 1,2,3 ,4,10,l O-hexachlorol ,4,4a,5,8,8a-hexahydroendo-1,4-exo-5 ,8-dimethanonaphthalene [AL- DRIN] 1,2,3 ,4, l 0, l O-hexachloro-6,7-epoxy-l ,4,4a,5,6,7,8- ,8a-octahydro-exo-l ,4,endo-5,8-dimethanonaphthalene [DIFLORIN] 1,2,3 ,4, l O, l O-hexachloro-5,7-epoxy-l ,4,4a,5,6,7,8-

,8a-octyhydro-endo-end0-5,8-dimethanonaphthalene [ENDRIN] In addition to the properties cited hereinabove, the compounds of the formula I also act against representatives of the division Thallophyta. Thus a number of these compounds display bactericidal action; but they are also active against fungi, e.g. against phytopathogenic fugi belonging to the following calsses: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compounds of the formula 1 are also suitable for combating plant pathogenic nematodes.

The compounds of the formula 1 also possess in part herbicidal properties and are suitable in particular for combating grass-like and latifoliate weeds in various crop plant cultures. When used in high concentrations the new compounds act as total herbicides; on the other hand, when used in lower concentrations they act as selective herbicides. Deep rooted, difficultly combattable weeds which are one or more years old are successfully damaged in their growth or destroyed by the active substances of the formula I. The new active substances can be applied with the same good success before germination (preemergence) and after germination (postemergence). Thus meadow weeds, for example millet species (Panicum spp.), mustard species (Chenopodiaceae), slender foxtail (alopecurus spp.) and other foxtail species, e.g. Amarantus spp., grasses, e.g. Lolium spp., Compositae, e.g. Taraxacum spp., camomile species (Matricaria spp.), are destroyed or hindered in their growth without damage being caused 10 to cultivated plants, such as cereals, maize, cotton, sorghum, soya beans and sugar beet. The rates of application vary and are dependent on the time of application; they are between 0.1 to 10 kg of active substance per hectare, on preemergence application up to V1 kg per hectare and on postemergence 3 to 10 kg of active substance per hectare. In order to totally destroy entire crops of weeds, for example on fallow land neighbouring on the cultivated areas, it is necessary to use more than 10 kg per hectare. The usual crop rotation may proceed on application of the new active substances without any detrimental effects.

In order to broaden the activity spectrum it is also possible to admix the active substances of the formula I with other herbicides, for example from the series of the triazines, such as halogeno-diamino-s-triazines, alkoxyand alkylthio-diamino-s-triazines, triazoles, diazines, such as uraciles, aliphatic carboxylic acids and halocarboxylic acids, halogenated benzoic acids and phenylacetic acids, aryloxyalkanecarbocylic acids, hydrazides, amides, nitriles, esters of such carboxylic acids, carbamic and thiocarbamic esters, ureas etc.

The compounds of the formula I may be usedas pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formulation which is commonly employed in application technology. Mention may also be made of cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the following forms.

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous. granules.

Liquid forms:

a. active substances which are dispersible in water: wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly or in admixture with one another.

Granules can be very-easily manufactured by dissolving an active substance of the formula 1 in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S10

1 1 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances ofthe formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favable predeterminable absorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/liter can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilise the active substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts ofligni n sulphonic acid, in addition, alkylaryl sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexi2 adecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salts of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives cited hereinabove in such a manner that, the size of the solid particles does not exceed 0.02 to 0.04 p. in Wettable powders, and 0.03 ,u. in pastes. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, or ganic solvents, and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene, dimethyl sulphoxide, and mineral oil fraction which boil between 120 and 350C. The solvents must be practically odourless, not phytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substances, or several active substances of the general formula I, are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, singly or in admixture with each other, can be used as organic solvents. i

The content of active substance in the above described agents is between 0.l% to in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

DUSTS The following substances are used to manufacture (a) a 5% and (b) a 2% dust:

a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

GRANULES The following substances are used to produce 5% granules:

5 parts of active substance. 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo.

WETTABLE POWDER The following constituents are used of the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

a) 40 parts of active substance,

parts of sodium lignin sulphonate. 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid. b) 25 parts of active substance,

4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c) 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin. d) parts of active substance.

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

EMULSIFIABLE CONCENTRATES The following substances are used to produce (a) a 10% and (b) a 25% emulsifiable concentrate:

a) 10 parts of active substance,

3.4 parts of epoxidised vegetable 011,

13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b) 25 parts of active substance,

2.5 parts of epoxidised vegetable oil, 10 parts of alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide, 57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

SPRAY The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorohydrin,

94 parts of benzine (boiling limits 160190C).

EXAMPLE 1 O-ethyl-S-propyl-S-(2methoxyethylcarbamoylmetltYD-dithiophosphoric ester 14 30.3 g of chloroacetic-N-(2-methoxyethyl)-amide and 41 g-ofthe potassium salt of O-ethyl-S-propyl-thiophosphoric acid are stirred overnight at room temperature in 200 ml of acetonitrile and the mixture is subsequently heated to the boil under reflux for 3 hours.

After the mixture has cooled, the salts are filtered off with suction, the solvent is evaporated in vacuo and the residue is taken up in ml of methylene chloride and washed in succession with 30 ml of normal sodium hydroxide solution and 30 ml of water. The solvent is distilled off in vacuo at 4050C bath temperature to leave as residue 41.5 g of phosphorus ester of the above described formula with a refraction of r1 1.5115. The following compounds are also manufactured in analogous manner:

Insecticidal ingest poison action Cotton plants were sprayed with a 0.05% aqueous ac tive substance emulsion (obtained from 10% emulsifiable concentrate).

After the spray coating had dried, the cotton plants were populated with S podoptera littoralis or H eliothis virescens larvae (L The test was carried out at 24C and 60% relative humidity.

In the above test, the compounds according to Example l displayed good insecticidal ingest poison action against Spodoptera and Heliothis larvae.

EXAMPLE 3 Action against C hilo suppressalis Six rice plants at a time of the variety Caloro were transplanted in plastic pots (diameter at the top 17 cm) and r red to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L 3 4 mm in lenght) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action ensued 10 days after application of the granules.

In the above test, the compounds according to Example 1 acted against Chilo suppressalis.

EXAMPLE 4 Action against ticks A. Rhipicephalus bursa 1 Five adult ticks or 50 tick larvae were counted into a test tube and immersed for l to 2 minutes in 2 ml'of an aqueous emulsion series each containing 100, 10, l and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and stood on its head so as to enable the cotton wool to absorb the active substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae) Tests were carried out with 20 sensitive and 20 OP resistent larvae with a dilution series analogous to that used in Test A. (The resistance refers to the tolerability of diazinon).

In these tests, the compounds according to Example I acted against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistant larvae of B- philus microplus.

EXAMPLE 5 Acar icidal action Phaseolus vulgaris (plants) were overlaid with an infested piece of leaf from a mass culture of Tetranychus urlicae 12 hours before the test for acaricidal action. The mobile stages which had spread over the plants were sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth did not run off. The number of living and dead larvae,

16 adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result was expressed in percentages. During the interim, the treated plants "were kept in greenhouse compartments at 25C.

In the above test, the compounds according to Example 1 acted against adults larvae and eggs of T etranychus urticae.

EXAMPLE 6 Action against soil nematodes stances according to Example I display good action against Meloidgyne Avenaria.

I claim: 1. A compound of the formula wherein R represents hydrogen or methyl. 

1. A COMPOUND OF THE FORMULA 